EP0100788B1 - Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether - Google Patents

Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether Download PDF

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Publication number
EP0100788B1
EP0100788B1 EP82107481A EP82107481A EP0100788B1 EP 0100788 B1 EP0100788 B1 EP 0100788B1 EP 82107481 A EP82107481 A EP 82107481A EP 82107481 A EP82107481 A EP 82107481A EP 0100788 B1 EP0100788 B1 EP 0100788B1
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Prior art keywords
catalyst
trifluoro
ether
reaction
chloroethyl
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EP82107481A
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German (de)
French (fr)
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EP0100788A1 (en
Inventor
Shuichi Takamatsu
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Daikin Industries Ltd
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Daikin Kogyo Co Ltd
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Priority to EP82107481A priority Critical patent/EP0100788B1/en
Priority to DE8282107481T priority patent/DE3276530D1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C07C43/123—Saturated ethers containing halogen both carbon chains are substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to an improved process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether by reacting 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride.
  • 1,1,2-Trifluoro-2-chloroethyl difluoromethyl ether useful as an anesthetic, has been prepared by fluorinating 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride in a liquid phase in the presence of an antimony (V) catalyst or a tin (IV) catalyst (cf. Japanese Patent Publication (unexamined) No. 3,606/1973 and its US-counterpart US-A 3 469 011).
  • V antimony
  • IV tin
  • this process is disadvantageous in that the reaction can hardly be carried out continuously.
  • the catalyst is, after completion of the reaction, to be decomposed with water and removed.
  • 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether can be prepared in a good yield by reacting in a gaseous phase 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride.
  • the present invention provides a process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether by reacting 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride in the presence of a fluorination catalyst, characterised in that the reaction is carried out in a gaseous state at a temperature of from the boiling point of the starting ether to 400°C in the absence of any catalyst or in the presence of a catalyst selected from the group consisting of oxyfluorides of molybdenum and fluorides and oxyfluorides of chromium and thallium.
  • the use of the catalyst is essential for the practical rate of the reaction.
  • the fluorination is preferably carried out at a temperature of from 0°C to 10°C, but at a higher temperature, a side reaction may proceed.
  • the gas phase fluorination according to the present invention can well proceed even in the absence of any catalyst and proceeds more advantageously in the presence of a catalyst.
  • the fluorination may be carried out not only at a low temperature but also at a higher temperature with a good yield:
  • the fluorination of the invention can be carried out continuously with a high yield.
  • a catalyst When a catalyst is used, continuous operation is possible over a long period of time without producing any waste of the catalyst.
  • the fluorination of the present invention may be carried out in the presence or absence of a catalyst, and the desired fluorinated product is obtainable in a good yield. Practically and usually, the catalyst is used, whereby the reaction is accelerated.
  • the catalysts used are oxyfluorides of molybdenum, and fluorides and oxyfluorides of chromium and thallium. These may be used as such or deposited on a carrier, such as activated charcoal, alumina, fluorinated alumina, calcium fluoride, sodium fluoride and magnesium fluoride. Strong Lewis acids such as titanium tetrafluoride are not favorable, because a clear tendency to lower the yield is observed.
  • the reaction temperature is from the boiling point of 1,1,2-trifiuor p- 2-ch)oroethyi dichloromethyl ether (about 115°C at atmospheric pressure) to 400°C, particularly from 200°C to 400°C when the catalyst is not used, and from said boiling point to 350°C when the catalyst is used.
  • the reaction temperature is preferred to be as low as possible in the said range.
  • the reaction pressure is not critical and preferably from 0.5 to 10 atm.
  • the molar ratio of the starting ether and hydrogen fluoride is not critical and may be usually from 1:2 to 1:20.
  • the space velocity is also not critical and may be usually from 10 to 10,000 hr- 1 .
  • 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether and hydrogen fluoride are reacted in a molar ratio of 1:16 in the absence of the catalyst at 245°C with a space velocity of 31 hr- 1 , the yield is 69.6%.
  • the same starting materials as above are reacted in the same molar ratio as above in the presence of MoO x Fy deposited on activated charcoal at 160°C with a space velocity of 474 hr- 1 , the yield is 92.1 %.
  • reaction may proceed according to the following reaction formula: i
  • an intermediate 1,1,2-trifluoro-2-chloroethyl chlorofluoromethyl ether may be contained in the resulting reaction mixture and can easily be recovered on separation of the desired product 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether from the reaction mixture by distillation.
  • the recovered intermediate may be further fluorinated to produce the desired product, which improves the yield.
  • Molybdenum trioxide (5.5 g) was dissolved in 28% aqueous ammonia (50 g) by heating. To the resulting solution, activated charcoal (43 g, about 100 ml) was added, and then water and ammonia were evaporated off under reduced pressure. The residue was charged into the middle portion of a reaction tube made of Hastelloy C (trade name) having an inner diameter of 1 inch, which was placed in an electric furnace, heated in a stream of nitrogen at 300°C for about 5 hours to remove water and ammonia completely and then treated with anhydrous hydrogen fluoride at 300°C for about 5 hours to produce a MoO x Fy catalyst.
  • Hastelloy C trade name
  • 1,1,2-Trifluoro-2-chloroethyl dichloromethyl ether and anhydrous hydrogen fluoride in a molar ratio of 1: 16 were passed through in a preheating mixing tube and then the bed of the catalyst in the reaction tube kept at 160°C with a space velocity of 474 hr- 1 .
  • the gaseous reaction mixture was passed through ice water and trapped with a dry-ice/acetone cooled trap.
  • Example 2 In the same manner as in Example 1 but using the catalyst, the space velocity and the reaction temperature as shown in table 1, the reaction was carried out.
  • MoO x F y /activated charcoal was the same as prepared in Example 1;
  • AIF 3 which was used for comparison, was a commercial available one; and
  • erO x Fy and TIO x Fy were prepared by treating Cr 2 0 3 or Cr0 3 and TI 2 0 3 with anhydrous hydrogen fluoride for several hours at a temperature of from 200°C to 450°C and of 150°C, respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  • The present invention relates to an improved process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether by reacting 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride.
  • 1,1,2-Trifluoro-2-chloroethyl difluoromethyl ether, useful as an anesthetic, has been prepared by fluorinating 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride in a liquid phase in the presence of an antimony (V) catalyst or a tin (IV) catalyst (cf. Japanese Patent Publication (unexamined) No. 3,606/1973 and its US-counterpart US-A 3 469 011). However, this process is disadvantageous in that the reaction can hardly be carried out continuously. It is also disadvantageous that the catalyst is, after completion of the reaction, to be decomposed with water and removed.
  • As a result of the extensive study, it has been found that 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether can be prepared in a good yield by reacting in a gaseous phase 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride.
  • Accordingly, the present invention provides a process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether by reacting 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride in the presence of a fluorination catalyst, characterised in that the reaction is carried out in a gaseous state at a temperature of from the boiling point of the starting ether to 400°C in the absence of any catalyst or in the presence of a catalyst selected from the group consisting of oxyfluorides of molybdenum and fluorides and oxyfluorides of chromium and thallium.
  • In the said conventional liquid-phase fluorination process, the use of the catalyst is essential for the practical rate of the reaction. Further, the fluorination is preferably carried out at a temperature of from 0°C to 10°C, but at a higher temperature, a side reaction may proceed. To the contrary, the gas phase fluorination according to the present invention can well proceed even in the absence of any catalyst and proceeds more advantageously in the presence of a catalyst. Further, the fluorination may be carried out not only at a low temperature but also at a higher temperature with a good yield:
  • The fluorination of the invention can be carried out continuously with a high yield. When a catalyst is used, continuous operation is possible over a long period of time without producing any waste of the catalyst. These make the process of the invention advantageous in the industry.
  • As stated above, the fluorination of the present invention may be carried out in the presence or absence of a catalyst, and the desired fluorinated product is obtainable in a good yield. Practically and usually, the catalyst is used, whereby the reaction is accelerated.
  • The catalysts used are oxyfluorides of molybdenum, and fluorides and oxyfluorides of chromium and thallium. These may be used as such or deposited on a carrier, such as activated charcoal, alumina, fluorinated alumina, calcium fluoride, sodium fluoride and magnesium fluoride. Strong Lewis acids such as titanium tetrafluoride are not favorable, because a clear tendency to lower the yield is observed.
  • The reaction temperature is from the boiling point of 1,1,2-trifiuorp-2-ch)oroethyi dichloromethyl ether (about 115°C at atmospheric pressure) to 400°C, particularly from 200°C to 400°C when the catalyst is not used, and from said boiling point to 350°C when the catalyst is used. At too high a reaction temperature, the ether linkage is broken to lower the yield. Thus, the reaction temperature is preferred to be as low as possible in the said range.
  • The reaction pressure is not critical and preferably from 0.5 to 10 atm.
  • The molar ratio of the starting ether and hydrogen fluoride is not critical and may be usually from 1:2 to 1:20. The space velocity is also not critical and may be usually from 10 to 10,000 hr-1. When, for example, 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether and hydrogen fluoride are reacted in a molar ratio of 1:16 in the absence of the catalyst at 245°C with a space velocity of 31 hr-1, the yield is 69.6%. When the same starting materials as above are reacted in the same molar ratio as above in the presence of MoOxFy deposited on activated charcoal at 160°C with a space velocity of 474 hr-1, the yield is 92.1 %.
  • In the fluorination of the invention, the reaction may proceed according to the following reaction formula: i
    Figure imgb0001
  • Therefore, an intermediate 1,1,2-trifluoro-2-chloroethyl chlorofluoromethyl ether may be contained in the resulting reaction mixture and can easily be recovered on separation of the desired product 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether from the reaction mixture by distillation. The recovered intermediate may be further fluorinated to produce the desired product, which improves the yield.
  • The present invention will be hereinafter explained in detail by the following Examples.
    • Example 1
  • Molybdenum trioxide (5.5 g) was dissolved in 28% aqueous ammonia (50 g) by heating. To the resulting solution, activated charcoal (43 g, about 100 ml) was added, and then water and ammonia were evaporated off under reduced pressure. The residue was charged into the middle portion of a reaction tube made of Hastelloy C (trade name) having an inner diameter of 1 inch, which was placed in an electric furnace, heated in a stream of nitrogen at 300°C for about 5 hours to remove water and ammonia completely and then treated with anhydrous hydrogen fluoride at 300°C for about 5 hours to produce a MoOxFy catalyst.
  • 1,1,2-Trifluoro-2-chloroethyl dichloromethyl ether and anhydrous hydrogen fluoride in a molar ratio of 1: 16 were passed through in a preheating mixing tube and then the bed of the catalyst in the reaction tube kept at 160°C with a space velocity of 474 hr-1. The gaseous reaction mixture was passed through ice water and trapped with a dry-ice/acetone cooled trap. Gas chromatographic analysis of the trapped reaction mixture showed that the yields of 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether, of 1,1,2-trifluoro-2-chloroethyl chlorofluoromethyl ether and of 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether were respectively 92.1%, 1.8% and 0.2%.
    • Examples 2 to 6
  • In the same manner as in Example 1 but using the catalyst, the space velocity and the reaction temperature as shown in table 1, the reaction was carried out. Among the catalysts, MoOxFy/activated charcoal was the same as prepared in Example 1; AIF3, which was used for comparison, was a commercial available one; and erOxFy and TIOxFy were prepared by treating Cr203 or Cr03 and TI203 with anhydrous hydrogen fluoride for several hours at a temperature of from 200°C to 450°C and of 150°C, respectively.
    Figure imgb0002

Claims (4)

1. A process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether by reacting 1,1,2-trifluoro-2-chloroethyl dichloromethyl ether with hydrogen fluoride in the presence of a fluorination catalyst, characterised in that the reaction is carried out in a gaseous state at a temperature of from the boiling point of the starting ether to 400°C in the absence of any catalyst or in the presence of a catalyst selected from the group consisting of oxyfluorides of molybdenum, and fluorides and oxyfluorides of chromium and thallium.
2. The process according to claim 1, wherein the reaction is carried out at a temperature of from 200°C to 400°C in the absence of a catalyst.
3. The process according to claim 1, wherein the reaction is carried out at a temperature of from the boiling point of the starting ether to 350°C in the presence of the catalyst.
4. The process according to claim 3, wherein the catalyst is one selected from the group consisting of oxyfluorides of molybdenum, chromium and thallium.
EP82107481A 1982-08-17 1982-08-17 Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether Expired EP0100788B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP82107481A EP0100788B1 (en) 1982-08-17 1982-08-17 Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether
DE8282107481T DE3276530D1 (en) 1982-08-17 1982-08-17 Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether

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Application Number Priority Date Filing Date Title
EP82107481A EP0100788B1 (en) 1982-08-17 1982-08-17 Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether

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EP0100788B1 true EP0100788B1 (en) 1987-06-10

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* Cited by examiner, † Cited by third party
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US4620040A (en) * 1985-03-18 1986-10-28 Occidental Chemical Corporation Process for the preparation of α-α-α-trifluoroanisoles
DE4314498A1 (en) * 1993-05-03 1994-11-10 Bayer Ag Process for the preparation of perfluoroalkoxy (alkylthio) benzenes

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US3469011A (en) * 1966-10-03 1969-09-23 Air Reduction 1,1,2-trifluoro-2-chloroethyl-difluoromethyl ether as an anesthetic agent
DE2344442A1 (en) * 1973-09-04 1975-04-03 Hoechst Ag PROCESS FOR THE PRODUCTION OF 1-CHLORO2,2,2-TRIFLUORAETHYL-DIFLUOROMETHYLAETHER

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DE3276530D1 (en) 1987-07-16

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